Catalysts having selected pore size distributions, method of making such catalysts, methods of producing a crude product, products obtained from such methods, and uses of products obtained

ABSTRACT

A catalyst and a method of preparation of said catalyst is described herein. The catalyst includes one or more metals from Columns 6-10 of the Periodic Table and/or one or more compounds of one or more metals from Columns 6-10 of the Periodic Table, a pore size distribution with a median pore diameter ranging from 105 Å to 150 Å, with 60% of the total number of pores in the pore size distribution having a pore diameter within 60 Å of the median pore diameter, with at least 50% of its pore volume in pores having a pore diameter of at most 600 Å, and between 5% and 25% of its pore volume in pores having a pore diameter between 1000 Å and 5000 Å. Methods of producing said catalyst are described herein. Crude products and products made from said crude products are described herein.

This patent application claims the benefit of U.S. ProvisionalApplication 61/043926, filed Apr. 10, 2008, which is incorporated hereinby reference

FIELD OF THE INVENTION

The present invention relates to catalysts having selected pore sizedistributions, method of making such catalysts, methods of producing acrude product, products obtained from such methods, and uses of productsobtained.

BACKGROUND OF THE INVENTION

Crude oils that have one or more unsuitable properties that do not allowthe crudes to be economically transported, or processed usingconventional facilities, are commonly referred to as “disadvantagedcrudes”. Disadvantaged crudes may have a high viscosity that renders thedisadvantaged crude undesirable for conventional transportation and/ortreatment facilities. Disadvantaged crudes having high viscosities,additionally, may also include hydrogen deficient hydrocarbons. Whenprocessing disadvantaged crudes having hydrogen deficient hydrocarbons,consistent quantities of hydrogen may need to be added to inhibit cokeformation, particularly if elevated temperatures and high pressure areused to process the disadvantaged crude. Hydrogen, however, is costly toproduce and/or costly to transport to treatment facilities.

Conventional methods of reducing the high viscosity of the disadvantagedcrude include contacting the disadvantaged crude at elevatedtemperatures and pressure with hydrogen in the presence of a catalyst.Sediment formed during processing may accumulate in the larger pores ofthe catalyst while viscosity and/or other properties are reduced bycontact of the feed with the active metals in the smaller pores of thecatalyst that the sediment and/or large compounds contributing toviscosity can not enter. Disadvantages of conventional catalysts arethat they require significant amounts of hydrogen in order to processthe hydrogen deficient hydrocarbons and that the larger pores of thecatalyst become filled. Thus, the activity of the catalyst is diminishedand the life of the catalyst is reduced. To counteract the diminishedactivity and/or increase throughput per volume of feed, the catalyst maycontain a significant amount of metal and/or combination of metals. Asmore metal is used in a catalyst, the pores of the catalyst becomefilled resulting in catalyst that have that are diminished pore size dueto the metal occupying space in the pore. To accommodate more metal,catalysts with larger pore diameters may be made, however, an increasein pore diameter may reduce the surface area of the catalyst.

It would be desirable to have a process and/or catalyst for reducing theviscosity of a disadvantaged crude at selected temperatures and minimalpressures. Such a catalyst could be used at elevated temperatures andminimal pressures.

U.S. Pat. No. 4,225,421 to Hensley; U.S. Pat. No. 5,928,499 to Sherwood,Jr. et al U.S. Pat. No. 6,554,994 to Reynolds et al., U.S. Pat. No.6,436,280 to Harle et al., U.S. Pat. No. 5,928,501 to Sudhakar et al.,U.S. Pat. No. 4,937,222 to Angevine et al., U.S. Pat. No. 4,886,594 toMiller, U.S. Pat. No. 4,746,419 to Peck et al., U.S. Pat. No. 4,548,710to Simpson, U.S. Pat. No. 4,525,472 to Morales et al., U.S. Pat. No.4,499,203 to Toulhoat et al., U.S. Pat. No. 4,389,301 to Dahlberg etal., and U.S. Pat. No. 4,191,636 to Fukui et al. describe variousprocesses, systems, and catalysts for processing crudes and/ordisadvantaged crudes.

U.S. Published Patent Application Nos. 20050133414 through 20050133418to Bhan et al.; 20050139518 through 20050139522 to Bhan et al.,20050145543 to Bhan et al., 20050150818 to Bhan et al., 20050155908 toBhan et al., 20050167320 to Bhan et al., 20050167324 through 20050167332to Bhan et al., 20050173301 through 20050173303 to Bhan et al.,20060060510 to Bhan; 20060231465 to Bhan; 20060231456 to Bhan;20060234876 to Bhan; 20060231457 to Bhan and 20060234877 to Bhan;20070000810 to Bhan et al.; 20070000808 to Bhan; 20070000811 to Bhan etal., and U.S. patent application Ser. Nos. 11/866,909; 11/866,916;11/866,921 through 11/866,923; 11/866,926; 11/866,929 and 11/855,932 toBhan et al., filed Oct. 3, 2007, are related patent applications anddescribe various processes, systems, and catalysts for processing crudesand/or disadvantaged crudes.

U.S. Pat. No. 4,225,421 to Hensley et al. describes a catalyst having abimodal pore structure and improved effectiveness in the desulfurizationand demetallation of metal-containing hydrocarbon streams. This catalysthas a surface area between 140 and 300 m²/g, 60-95% of its pore volumein pores having a pore diameter from 2-200 Å, 1-15% of its pore volumein pores having a pore diameter from 200-600 Å, and 3-30% of its porevolume in pores having a pore diameter from 600-10,000 Å as determinedusing nitrogen adsorption methods. Operating pressures range from 5.5MPa to 20.7 MPa. Operating temperatures range from 371° C. to 454° C. InTables I through III, the average pore diameter of the catalysts rangefrom 137 Å to 162 Å.

U.S. Pat. No. 5,928,499 to Sherwood, Jr. et al. describes a process forhydrotreating a hydrocarbon feed containing components boiling above1000° F. and sulfur, metals and carbon residue utilizing a heterogeneouscatalyst having a specified pore size distribution, median pore diameterby surface area and pore mode by volume, to give a product containing adecreased content of components boiling above 1000° F., decreasedsulfur, metals and carbon residue is disclosed. The catalyst includes anporous alumina support containing less than or equal to 2.5 wt % silicaon a finished catalyst basis, and bearing 2.2 wt% to 6 wt % of a GroupVIII metal oxide, 7 wt % to 24 wt % of a Group VIB metal oxide andpreferably less than 0.2 wt % of a phosphorous oxide. The catalyst maybe characterized as having a total surface area of 215 to 245 m²/g, atotal pore volume of 0.82 to 0.98 cc/g, a median pore diameter bysurface area of 91 to 104 Å, and a pore diameter distribution in which22.0 to 33.0% of the total pore volume is present as macropores of adiameter greater than 250 Å, 67.0 to 78.0% of the total pore volume ispresent as micropores of a diameter less that 250 Å. The pore volumeswere determined using mercury porosity measurements. Operating pressuresrange from 1800-2500 psig (approximately 12 MPa to 17 MPa. Operatingtemperatures range from 700° F. to 900° F. (371° C. to 384° C.).

U.S. Pat. No. 5,221,656 to Clark et al. describes a hydroprocessingcatalyst that has a surface area of greater than 220 m²/g, a pore volumeof about 0.23-0.30 cc/g in pores greater than about 600 radius Å, anaverage pore radius of about 30-70 Å in pores less than 600 Å, and anincremental pore volume curve with a maximum at about 25-50 Å radius.The hydrocarbon feed is contacted with the catalyst at an operatingpressures range of about 13.8 MPa (2000 psig) and a temperature of 421°C. (790° F.).

As outlined above, there has been considerable effort to develop methodsand systems to economically convert disadvantaged crudes to useableproducts. It would be advantageous to be able to convert crudes with ahigh viscosity, and therefore a low economic value, into a crude producthaving a decreased viscosity content by contacting the crudes with acatalyst with a minimal amount of sediment formation. It would also beadvantageous to consume a minimal amount of hydrogen during processing.The resulting crude product may, thereafter, be converted to selectedhydrocarbon products using conventional hydrotreating catalysts.

SUMMARY OF THE INVENTION

It has now been found that a hydrocarbon feed with a high viscosity canbe converted into a crude product having a decreased viscosity whilstsediment formation is kept low by using a specific catalyst. As a resultthe catalyst may have a long useful life. In addition, it has been foundthat such a conversion may be carried out with minimal hydrogenconsumption.

Accordingly, in some embodiments, the invention provides a method ofmaking a catalyst, comprising:

co-mulling one or more metals from Columns 6-10 of the Periodic Tableand/or one or more compounds of one or more metals from Columns 6-10 ofthe Periodic Table with a support to produce a metal/supportcomposition; and

calcining the metal/support composition at temperatures ranging from315° C. to 760° C. to provide a calcined catalyst with a pore sizedistribution with a median pore diameter ranging from 105 Å to 150 Åwith at least 60% of the total number of pores in the pore sizedistribution having a pore diameter within 60 Å of the median porediameter, with at least 50% of its pore volume in pores having a porediameter of at most 600 Å, and between 5% and 25% of its pore volume inpores having a pore diameter between 1000 Å and 5000 Å, wherein porediameters and pore volumes are as measured by ASTM Method D4284.

In some embodiments, the invention provides a catalyst comprising:

one or more metals from Columns 6-10 of the Periodic Table and/or one ormore compounds of one or more metals from Columns 6-10 of the PeriodicTable; wherein the catalyst has a median pore diameter ranging from 105Å to 150 Å with at least 60% of the total number of pores in the poresize distribution having a pore diameter within at least 60 Å of themedian pore diameter, with at least 50% of its pore volume in poreshaving a pore diameter of at most 600 Å, and between 5% and 25% of itspore volume in pores having a pore diameter between 1000 Å and 5000 Å,wherein pore diameters and pore volumes are as measured by ASTM MethodD4284.

In some embodiments, the invention provides a method of producing acrude product, comprising:

contacting a hydrocarbon feed with one or more catalysts to produce atotal product that includes the crude product, wherein at least one ofthe catalysts comprises one or more metals from Columns 6-10 of thePeriodic Table and/or one or more compounds of one or more metals fromColumns 6-10 of the Periodic Table; wherein the Column 6-10 metalcatalyst has a median pore diameter ranging from 105 Å to 150 Å with atleast 60% of the total number of pores in the pore size distributionhaving a pore diameter within at least 60 Å of the median pore diameter,with at least 50% of its pore volume in pores having a pore diameter ofat most 600 Å, and between 5% and 25% of its pore volume in pores havinga pore diameter between 1000 Å and 5000 Å, wherein surface area is asdetermined by ASTM Method D3663 and pore diameters and pore volumes areas measured by ASTM Method D4284; and pore diameters and pore volumesare as measured by ASTM Method D4284.

The invention also provides a crude product produced by the methoddescribed herein.

In some embodiments, the invention further provides a hydrocarboncomposition comprising:

a total Ni/Fe/V content of at least 150 wtppm as determined by ASTMMethod D5708;

a residue content of at least 0.1 grams per gram of hydrocarboncomposition as determined by ASTM Method D5307;

a distillate content of at least 0.1 grams per gram of hydrocarboncomposition as determined by ASTM Method D5307;

an oxygen content of at most 0.1 grams per gram of hydrocarboncomposition, as determined by ASTM Method E385; and

a micro-carbon residue content of at least 0.05 grams per gram ofhydrocarbon composition as determined by ASTM Method D4530, and

a viscosity of at most 100 cSt at 37.8° C., wherein viscosity is asdetermined by ASTM Method D445.

In some embodiments, the invention provides a transportation fuelcomprising the crude product or one or more distillate fractions madefrom the crude product described herein.

In some embodiments, the invention provides a diluent comprising thecrude product or one or more distillate fractions made from the crudeproduct as described herein.

BRIEF DESCRIPTION OF THE DRAWINGS

The invention has been illustrated by the following figure:

FIG. 1 is a schematic of an embodiment of a contacting system.

DETAILED DESCRIPTION OF THE INVENTION

Terms used herein are defined as follows.

“ASTM” refers to American Standard Testing and Materials.

“API gravity” refers to API gravity at 15.5° C. (60° F.). API gravity isas determined by ASTM Method D6822.

Atomic hydrogen percentage and atomic carbon percentage of thehydrocarbon feed and the crude product are as determined by ASTM MethodD5291.

“Bimodal catalyst” refers to a catalyst in which at least the majorityof the pore volume is distributed in two statistical distributions ofpore diameters, each statistical distribution having a significant peakwhen displayed on a pore volume versus pore diameter plot. For example,a bimodal catalyst may have 30% of its pore volume distributed in poreshaving a pore diameter between 50 Å and 100 Å (with a peak showing at 80Å) and 25% of its pore volume distributed in pores having a porediameter between 300 Å and 350 Å (with a peak showing at 320 Å).

Boiling range distributions for the hydrocarbon feed, the total product,and/or the crude product are as determined by ASTM Method D5307 unlessotherwise mentioned.

“C₅ asphaltenes” refers to asphaltenes that are insoluble in n-pentane.C₅ asphaltenes content is as determined by ASTM Method D2007.

“C₇ asphaltenes” refers to asphaltenes that are insoluble in n-heptane.C₇ asphaltenes content is as determined by ASTM Method D3279.

“Column X metal(s)” refers to one or more metals of Column X of thePeriodic Table and/or one or more compounds of one or more metals ofColumn X of the Periodic Table, in which X corresponds to a columnnumber (for example, 1-12) of the Periodic Table. For example, “Column 6metal(s)” refers to one or more metals from Column 6 of the PeriodicTable and/or one or more compounds of one or more metals from Column 6of the Periodic Table.

“Column X element(s)” refers to one or more elements of Column X of thePeriodic Table, and/or one or more compounds of one or more elements ofColumn X of the Periodic Table, in which X corresponds to a columnnumber (for example, 13-18) of the Periodic Table. For example, “Column15 element(s)” refers to one or more elements from Column 15 of thePeriodic Table and/or one or more compounds of one or more elements fromColumn 15 of the Periodic Table.

In the scope of this application, weight of a metal from the PeriodicTable, weight of a compound of a metal from the Periodic Table, weightof an element from the Periodic Table, or weight of a compound of anelement from the Periodic Table is calculated as the weight of metal orthe weight of element. For example, if 0.1 grams of MoO₃ is used pergram of catalyst, the calculated weight of the molybdenum metal in thecatalyst is 0.067 grams of molybdenum metal per gram of catalyst.

“Comulling” refers to contacting, combining, or pulverizing of at leasttwo substances together such that at least two substances are mixedthrough mechanical and physical forces. Comulling can form asubstantially uniform or homogeneous mixture. Comulling includes thecontacting of substances to yield a paste that can be extruded or formedinto extrudate particles, spheroids, pills, tablets, cylinders,irregular extrusions or loosely bound aggregates or clusters, by anyknown extrusion, molding tableting, pressing, pelletizing, or tumblingmethods. Comulling does not include impregnation methods in which aformed solid is immersed in a liquid or gas to absorb/adsorb componentsfrom the liquid or gas.

“Content” refers to the weight of a component in a substrate (forexample, a hydrocarbon feed, a total product, or a crude product)expressed as weight fraction or weight percentage based on the totalweight of the substrate. “Wtppm” refers to parts per million by weight.

“Distillate” refers to hydrocarbons with a boiling range distributionbetween 182° C. (360° F.) and 343° C. (650° F.) at 0.101 MPa. Distillatecontent is as determined by ASTM Method D5307.

“Heteroatoms” refers to oxygen, nitrogen, and/or sulfur contained in themolecular structure of a hydrocarbon. Heteroatoms content is asdetermined by ASTM Methods E385 for oxygen, D5762 for total nitrogen,and D4294 for sulfur. “Total basic nitrogen” refers to nitrogencompounds that have a pKa of less than 40. Basic nitrogen (“bn”) is asdetermined by ASTM Method D2896.

“Hydrocarbon feed/total product” refers to the mixture that contacts thecatalyst during processing.

“Hydrogen source” refers to a source of hydrogen and includes hydrogengas and/or a compound and/or compounds that when in the presence of ahydrocarbon feed and the catalyst react to provide hydrogen. A hydrogensource may include, but is not limited to, hydrocarbons (for example, C₁to C₄ hydrocarbons such as methane, ethane, propane, and butane), water,or mixtures thereof. A mass balance may be conducted to assess the netamount of hydrogen provided.

“LHSV” refers to a volumetric liquid feed rate per total volume ofcatalyst and is expressed in hours (h⁻¹). Total volume of catalyst iscalculated by summation of all catalyst volumes in the contacting zones,as described herein.

“Liquid mixture” refers to a composition that includes one or morecompounds that are liquid at standard temperature and pressure (25° C.,0.101 MPa, hereinafter referred to as “STP”), or a composition thatincludes a combination of one of more compounds that are liquid at STPwith one or more compounds that are solids at STP.

“Metals in metal salts of organic acids” refer to alkali metals,alkaline-earth metals, zinc, arsenic, chromium, or combinations thereof.A content of metals in metal salts of organic acids is as determined byASTM Method D1318.

“Micro-Carbon Residue” (“MCR”) content refers to a quantity of carbonresidue remaining after evaporation and pyrolysis of a substrate. MCRcontent is as determined by ASTM Method D4530.

“Molybdenum content in the hydrocarbon feed” refers to the content ofmolybdenum in the feed. The molybdenum content includes the amount ofinorganic molybdenum and organomolybdenum in the feed. Molybdenumcontent in the hydrocarbon feed is as determined by ASTM Method D5807.

“Monomodal catalyst” refers to a catalyst in which at least the majorityof the pore volume is distributed in one statistical distribution ofpore diameters, the statistical distribution having a significant peakwhen displayed on a pore volume versus pore diameter plot. For example,a monomodal catalyst may have 50% of its pore volume in pores having apore diameter between 70 Å and 300 Å (with a peak at 150 Å).

“Naphtha” refers to hydrocarbon components with a boiling rangedistribution between 38° C. (100° F.) and 182° C. (360° F.) at 0.101MPa. Naphtha content is as determined by ASTM Method D5307.

“Ni/V/Fe” refers to nickel, vanadium, iron, or combinations thereof.

“Ni/V/Fe content” refers to the content of nickel, vanadium, iron, orcombinations thereof. The Ni/V/Fe content includes inorganic nickel,vanadium and iron compounds and/or organonickel, organovanadium, andorganoiron compounds. The Ni/V/Fe content is as determined by ASTMMethod D5708.

“Nm³/m³” refers to normal cubic meters of gas per cubic meter ofhydrocarbon feed.

“Non-condensable gas” refers to components and/or mixtures of componentsthat are gases at STP.

“P (peptization) value” or “P-value” refers to a numeral value, whichrepresents the flocculation tendency of asphaltenes in the hydrocarbonfeed. P-Value is as determined by ASTM Method D7060.

“Periodic Table” refers to the Periodic Table as specified by theInternational Union of Pure and Applied Chemistry (IUPAC), November2003.

“Pore diameter”, “median pore diameter”, and “pore volume” refer to porediameter, median pore diameter, and pore volume, as determined by ASTMMethod D4284 (mercury porosimetry at a contact angle equal to 140°). Amicromeritics® A9220 instrument (Micromeritics Inc., Norcross, Ga.,U.S.A.) may be used to determine these values.

“Residue” refers to components that have a boiling range distributionabove 538° C. (1000° F.), as determined by ASTM Method D5307.

“Sediment” refers to impurities and/or coke that are insoluble in thehydrocarbon feed/total product mixture. Sediment is as determined byASTM Method D4807. Sediment may also be determined by the Shell HotFiltration Test (“SHFST”) as described by Van Kernoort et al. in theJour. Inst. Pet., 1951, pages 596-604.

“SCFB” refers to standard cubic feet of gas per barrel of hydrocarbonfeed.

“Surface area” of a catalyst is as determined by ASTM Method D3663.

“VGO” refers to hydrocarbons with a boiling range distribution between343° C. (650° F.) and 538° C. (1000° F.) at 0.101 MPa. VGO content is asdetermined by ASTM Method D5307.

“Viscosity” refers to kinematic viscosity at 37.8° C. (100° F.).Viscosity is as determined using ASTM Method D445.

“Hydrocarbon feed” refers to a feed that includes hydrocarbons.Hydrocarbon feed may include, but is not limited to, crudes,disadvantaged crudes, stabilized crudes, hydrocarbons obtained fromrefinery processes, or mixtures thereof. Examples of hydrocarbon feedobtained from refinery processes include, but are not limited to, longresidue, short residue, naphtha, gasoil and/or hydrocarbons boilingabove 538° C. (1000° F.), or mixtures thereof.

In one embodiment the hydrocarbon feed is a crude, herein also referredto as crude feed. Crude or crude feed refers to a feed of hydrocarbonswhich has been produced and/or retorted from hydrocarbon containingformations and which has not yet been distilled and/or fractionallydistilled in a treatment facility to produce multiple components withspecific boiling range distributions, such as atmospheric distillationmethods and/or vacuum distillation methods. Crudes may be solid,semi-solid, and/or liquid. Crudes may include for example coal, bitumen,tar sands or crude oil. The crude or crude feed may be stabilized toform a stabilized crude, also referred to as stabilized crude feed.Stabilization may include, but is not limited to, removal ofnon-condensable gases, water, salts, or combinations thereof from thecrude to form a stabilized crude. Such stabilization may often occur at,or proximate to, the production and/or retorting site.

Stabilized crudes have not been distilled and/or fractionally distilledin a treatment facility to produce multiple components with specificboiling range distributions (for example, naphtha, distillates, VGO,and/or lubricating oils). Distillation includes, but is not limited to,atmospheric distillation methods and/or vacuum distillation methods.Undistilled and/or unfractionated stabilized crudes may includecomponents that have a carbon number above 4 in quantities of at least0.5 grams of components per gram of crude. Examples of stabilized crudesinclude whole crudes, topped crudes, desalted crudes, desalted toppedcrudes, or combinations thereof.

“Topped” refers to a crude that has been treated such that at least someof the components that have a boiling point below 35° C. at 0.101 MPa(95° F. at 1 atm) have been removed. Topped crudes may have a content ofat most 0.1 grams, at most 0.05 grams, or at most 0.02 grams of suchcomponents per gram of the topped crude.

Some stabilized crudes have properties that allow the stabilized crudesto be transported to conventional treatment facilities by transportationcarriers (for example, pipelines, trucks, or ships). Other crudes haveone or more unsuitable properties that render them disadvantaged.

Disadvantaged crudes may be unacceptable to a transportation carrierand/or a treatment facility, thus imparting a low economic value to thedisadvantaged crude. The economic value may be such that a reservoirthat includes the disadvantaged crude is deemed too costly to produce,transport, and/or treat.

The properties of the hydrocarbon feed, such as for example the crudesor disadvantaged crudes, may vary widely.

The hydrocarbon feed, such as for example a crude feed, may have aviscosity of at least 10 cSt at 37.8° C., at least 100 cSt, at least1000 cSt, or at least 2000 cSt at 37.8° C.

The hydrocarbon feed, such as for example a crude feed, may have an APIgravity of at most 19, at most 15, or at most 10. It may further have anAPI gravity of at least 5.

The hydrocarbon feed, such as for example a crude feed, may have a totalNi/V/Fe content of at least 0.00002 grams or at least 0.0001 grams ofNi/V/Fe per gram of hydrocarbon feed;

The hydrocarbon feed, such as for example a crude feed, may have a totalheteroatoms content of at least 0.005 grams of heteroatoms per gram ofhydrocarbon feed;

In some embodiments, the hydrocarbon feed has at least 0.001 grams ofoxygen containing compounds per gram of hydrocarbon feed, and whereinthe crude product has a oxygen containing compounds content of at most90% of the hydrocarbon feed oxygen-containing compounds content, whereinoxygen is as determined by ASTM Method E385.

The hydrocarbon feed, such as for example a crude feed, may have aresidue content of at least 0.01 grams of residue per gram ofhydrocarbon feed. In some embodiments, the hydrocarbon or crude feed mayinclude, per gram of feed, at least 0.2 grams of residue, at least 0.3grams of residue, at least 0.5 grams of residue, or at least 0.9 gramsof residue.

The hydrocarbon feed, such as for example a crude feed, may have pergram of hydrocarbon feed, a sulfur content of at least 0.005, at least0.01, or at least 0.02 grams.

The hydrocarbon feed, such as for example a crude feed, may have a C₅asphaltenes content of at least 0.04 grams or at least 0.08 grams of C₅asphaltenes per gram of hydrocarbon feed; and/or at least 0.02 grams orat least 0.04 grams of C₇ asphaltenes per gram of hydrocarbon feed.

The hydrocarbon feed, such as for example a crude feed, may have a MCRcontent of at least 0.002 grams of MCR per gram of hydrocarbon feed

The hydrocarbon feed, such as for example a crude feed, may have acontent of metals in metal salts of organic acids of at least 0.00001grams of metals per gram of hydrocarbon feed The hydrocarbon feed, suchas for example a crude feed, may further have a molybdenum content of atleast 0.1 wtppm;

The hydrocarbon feed, such as for example a crude feed, may further haveany kind of combination of the above mentioned properties.

The hydrocarbon feed, such as for example a crude feed, may include pergram of feed: at least 0.001 grams, at least 0.005 grams, or at least0.01 grams of hydrocarbons with a boiling range distribution between 95°C. and 200° C. at 0.101 MPa; at least 0.001 grams, at least 0.005 grams,or at least 0.01 grams of hydrocarbons with a boiling range distributionbetween 200° C. and 300° C. at 0.101 MPa; at least 0.001 grams, at least0.005 grams, or at least 0.01 grams of hydrocarbons with a boiling rangedistribution between 300° C. and 400° C. at 0.101 MPa; and at least0.001 grams, at least 0.005 grams, or at least 0.01 grams ofhydrocarbons with a boiling range distribution between 400° C. and 650°C. at 0.101 MPa.

In a further embodiment, the hydrocarbon feed, such as for example acrude feed, may include per gram of feed: at least 0.001 grams, at least0.005 grams, or at least 0.01 grams of hydrocarbons with a boiling rangedistribution of at most 100° C. at 0.101 MPa; at least 0.001 grams, atleast 0.005 grams, or at least 0.01 grams of hydrocarbons with a boilingrange distribution between 100° C. and 200° C. at 0.101 MPa; at least0.001 grams, at least 0.005 grams, or at least 0.01 grams ofhydrocarbons with a boiling range distribution between 200° C. and 300°C. at 0.101 MPa; at least 0.001 grams, at least 0.005 grams, or at least0.01 grams of hydrocarbons with a boiling range distribution between300° C. and 400° C. at 0.101 MPa; and at least 0.001 grams, at least0.005 grams, or at least 0.01 grams of hydrocarbons with a boiling rangedistribution between 400° C. and 650° C. at 0.101 MPa.

Some hydrocarbon feeds or crude feeds may include, per gram of feed, atleast 0.001 grams, at least 0.005 grams, or at least 0.01 grams ofhydrocarbons with a boiling range distribution of at most 100° C. at0.101 MPa, in addition to higher boiling components. Typically, adisadvantaged crude has, per gram of disadvantaged crude, a content ofsuch hydrocarbons of at most 0.2 grams or at most 0.1 grams.

Some hydrocarbon feeds or crude feeds may include, per gram of feed, atleast 0.001 grams, at least 0.005 grams, or at least 0.01 grams ofhydrocarbons with a boiling range distribution of at least 200° C. at0.101 MPa.

Some hydrocarbon feeds or crude feeds may include, per gram of feed, atleast 0.001 grams, at least 0.005 grams, or at least 0.01 grams ofhydrocarbons with a boiling range distribution of at least 650° C.

Examples of crudes that might be treated using the processes describedherein include, but are not limited to, crudes from of the followingregions of the world: U.S. Gulf Coast and southern California, CanadaTar sands, Brazilian Santos and Campos basins, Egyptian Gulf of Suez,Chad, United Kingdom North Sea, Angola Offshore, Chinese Bohai Bay,Venezuelan Zulia, Malaysia, and Indonesia Sumatra. The hydrocarbon feedmay be topped, as described herein.

Treatment of disadvantaged crudes may enhance the properties of thedisadvantaged crudes such that the crudes are acceptable fortransportation and/or treatment. The crude product resulting fromtreatment of the hydrocarbon feed, as described herein, is generallysuitable for transporting and/or treatment. Properties of the crudeproduct produced as described herein are closer to the correspondingproperties of West Texas Intermediate crude than the hydrocarbon feed,or closer to the corresponding properties of Brent crude, than thehydrocarbon feed, thereby enhancing the economic value of thehydrocarbon feed. Such crude product may be refined with less or nopre-treatment, thereby enhancing refining efficiencies. Pre-treatmentmay include desulfurization, demetallization, and/or atmosphericdistillation to remove impurities.

For example, in some embodiments, removal of at least a portion of theorganometallic compounds and/or metals from the hydrocarbon feed isperformed before the hydrocarbon feed is contacted with other catalysts.For example, a small amount of organomolybdenum and/or organocopper (forexample, at most 50 wtppm, at most 20 wtppm, or at most 10 wtppm) in ahydrocarbon feed may reduce the activity of a catalyst upon contact ofthe hydrocarbon feed with the catalyst.

The accumulation of deposits or insoluble components in the reactor maylead to a pressure change in the contacting zone, thus inhibitinghydrocarbon feed from passing through the contacting zone at desiredflow rates. For example, the inlet pressure of the contacting zone mayincrease rapidly over a short period of time as compared to the startingpressure. A rapid increase in pressure may indicate plugging of thecatalyst. A change in pressure of at least 3 MPa, at least 5 MPa, atleast 7 MPa, or at least 10 MPa over a short period of time may indicatecatalyst plugging.

Treatment of a hydrocarbon feed in accordance with embodiments describedherein may include contacting the hydrocarbon feed with the catalyst(s)in a contacting zone and/or combinations of two or more contactingzones. In a contacting zone, at least one property of a hydrocarbon feedmay be changed by contact of the hydrocarbon feed with one or morecatalysts relative to the same property of the hydrocarbon feed. In someembodiments, contacting is performed in the presence of a hydrogensource. In some embodiments, the hydrogen source is hydrogen gas. Insome embodiments, the hydrogen source is one or more hydrocarbons that,under certain contacting conditions, react to provide relatively smallamounts of hydrogen to compound(s) in the hydrocarbon feed.

FIG. 1 is a schematic of contacting system 100 that includes contactingzone 102. The hydrocarbon feed enters upstream contacting zone 102 viahydrocarbon feed conduit 104. A contacting zone may be a reactor, aportion of a reactor, multiple portions of a reactor, or combinationsthereof. Examples of a contacting zone include a stacked bed reactor, afixed bed reactor, an ebullating bed reactor, a continuously stirredtank reactor (“CSTR”), a fluidized bed reactor, a spray reactor, and aliquid/liquid contactor. Configuration of one or more contacting zonesis described in U.S. Published Patent Application No. 20050133414 toBhan et al., which is incorporated herein by reference. In certainembodiments, the contacting system is on or coupled to an offshorefacility. Contact of the hydrocarbon feed with catalyst(s) in contactingsystem 100 may be a continuous process or a batch process.

The contacting zone may include one or more catalysts (for example, twocatalysts). In some embodiments, contact of the hydrocarbon feed with afirst catalyst of the two catalysts may reduce viscosity of thehydrocarbon feed. Subsequent contact of the reduced viscosityhydrocarbon feed with the second catalyst may decrease metal contentand/or heteroatom content. In other embodiments, residue content, MCRcontent or combinations of these properties of the crude product changeby at least 10% relative to the same properties of the hydrocarbon feedafter contact of the hydrocarbon feed with one or more catalysts.

In certain embodiments, a volume of catalyst in the contacting zone isin a range from 10 vol % to 60 vol %, 20 vol % to 50 vol %, or 30 vol %to 40 vol % of a total volume of hydrocarbon feed in the contactingzone. In some embodiments, a slurry of catalyst and hydrocarbon feed mayinclude from 0.001 grams to 10 grams, 0.005 grams to 5 grams, or 0.01grams to 3 grams of catalyst per 100 grams of hydrocarbon feed in thecontacting zone.

Contacting conditions in the contacting zone may include, but are notlimited to, temperature, pressure, hydrogen source flow, hydrocarbonfeed flow, or combinations thereof. Contacting conditions in someembodiments are controlled to produce a crude product with specificproperties. Temperature in the contacting zone may range from 50° C. to500° C., preferably from 100° C. to 450° C. In some embodiments,temperature in a contacting zone may range from 350° C. to 450° C., from360° C. to 440° C., or from 370° C. to 430° C. LHSV of the hydrocarbonfeed will generally range from 0.1 h⁻¹ to 30 h⁻, 0.4 h⁻¹ to 25 h⁻, 0.5h⁻¹ to 20 h⁻¹, 1 h⁻¹ to 15 h⁻, 1.5 h⁻¹ to 10 h⁻¹, or 2 h⁻¹ to 5 h⁻¹. Insome embodiments, LHSV is at least 5 h⁻¹, at least 11 h⁻¹, at least 15h⁻¹, or at least 20 h⁻¹. A partial pressure of hydrogen in thecontacting zone may range from 0.1 MPa to 8 MPa, 1 MPa to 7 MPa, 2 MPAto 6 MPa, or 3 MPa to 5 MPa. In some embodiments, a partial pressure ofhydrogen may be at most 7 MPa, at most 6 MPa, at most 5 MPa, at most 4MPa, at most 3 MPa, or at most 3.5 MPa. In some embodiments, a partialpressure of hydrogen is the same as the total pressure of the contactingzone.

In embodiments in which the hydrogen source is supplied as a gas (forexample, hydrogen gas), a ratio (as determined at normal conditions of20° C. temperature and 1.013 bar pressure, also referred to as N m³/m³)of the gaseous hydrogen source to the hydrocarbon feed typically rangesfrom 0.1 Nm³/m³ to 100,000 Nm³/m³, 0.5 Nm³/m³ to 10,000 Nm³/m³, 1 Nm³/m³to 8,000 Nm³/m³, 2 Nm³/m³ to 5,000 Nm³/m³, 5 Nm³/m³ to 3,000 Nm³/m³, or10 Nm³/m³ to 800 Nm³/m³. The hydrogen source, in some embodiments, iscombined with carrier gas(es) and recirculated through the contactingzone. Carrier gas may be, for example, nitrogen, helium, and/or argon.The carrier gas may facilitate flow of the hydrocarbon feed and/or flowof the hydrogen source in the contacting zone(s). The carrier gas mayalso enhance mixing in the contacting zone(s). In some embodiments, ahydrogen source (for example, hydrogen, methane or ethane) may be usedas a carrier gas and recirculated through the contacting zone.

The hydrogen source may enter contacting zone 102 co-currently with thehydrocarbon feed via hydrocarbon feed conduit 104 or separately via gasconduit 106. In contacting zone 102, contact of the hydrocarbon feedwith a catalyst produces a total product that includes a crude product,and, in some embodiments, gas. In some embodiments, a carrier gas iscombined with the hydrocarbon feed and/or the hydrogen source in conduit106. The total product may exit contacting zone 102 and be transportedto other processing zones, storage vessels, or combinations thereof viaconduit 108.

In some embodiments, the total product may contain processing gas and/orgas formed during processing. Such gases may include, for example,hydrogen sulfide, carbon dioxide, carbon monoxide, excess gaseoushydrogen source, and/or a carrier gas. If necessary, the excess gas maybe separated from the total product and recycled to contacting system100, purified, transported to other processing zones, storage vessels,or combinations thereof. In some embodiments, gas produced during theprocess is at most 10 vol % based on total product, at most 5 vol %based on total product, or at most 1 vol % based the total productproduced. In some embodiments, minimal or non-detectable amounts of gasare produced during contact of the feed with the catalyst. In suchcases, the total product is considered the crude product.

In some embodiments, crude (either topped or untopped) is separatedprior to contact with one or more catalysts in contacting zone 102.During the separation process, at least a portion of the crude isseparated using techniques known in the art (for example, sparging,membrane separation, pressure reduction) to produce the hydrocarbonfeed. For example, water may be at least partially separated from thecrude. In another example, components that have a boiling rangedistribution below 95° C. or below 100° C. may be at least partiallyseparated from the crude to produce the hydrocarbon feed. In someembodiments, at least a portion of naphtha and compounds more volatilethan naphtha are separated from the disadvantaged crude.

In some embodiments, the crude product is blended with a crude that isthe same as or different from the hydrocarbon feed. For example, thecrude product may be combined with a crude having a different viscositythereby resulting in a blended product having a viscosity that isbetween the viscosity of the crude product and the viscosity of thecrude. In another example, the crude product may be blended with crudehaving a TAN, viscosity and/or API gravity that is different, therebyproducing a product that has a selected property that is between thatselected property of the crude product and the crude. The blendedproduct may be suitable for transportation and/or treatment. In someembodiments, disadvantaged crude is separated to form the hydrocarbonfeed. The hydrocarbon feed is then contacted with one or more catalyststo change a selected property of the hydrocarbon feed to form a totalproduct. At least a portion of the total product and/or at least aportion of a crude product from the total product may blended with atleast a portion of the disadvantaged crude and/or a different crude toobtain a product having the desired properties.

In some embodiments, the crude product and/or the blended product aretransported to a refinery and distilled and/or fractionally distilled toproduce one or more hydrocarbon fractions. The hydrocarbon fractions maybe processed to produce commercial products such as transportation fuel,lubricants, or chemicals. Blending and separating of the disadvantagedcrude and/or hydrocarbon feed, total product and/or crude product isdescribed U.S. Published Patent Application No. 20050133414 to Bhan etal.

In some embodiments, the crude product has a total molybdenum content ofat most 90%, at most 50%, at most 10%, at most 5%, or at most 3% of themolybdenum content of the hydrocarbon feed. In certain embodiments, thecrude product has a total molybdenum content ranging from 0.001 wtppm to1 wtppm, from 0.005 wtppm to 0.1 wtppm, or from 0.01 to 0.05 wtppm.

In some embodiments, the crude product has a copper content of at most90%, at most 50%, at most 10%, at most 5%, or at most 3% of the coppercontent of the hydrocarbon feed. In certain embodiments, the crudeproduct has a total copper content ranging from 0.001 wtppm to 1 wtppm,from 0.005 wtppm to 0.1 wtppm, or from 0.01 to 0.05 wtppm.

In some embodiments, the crude product has a total content of metals inmetal salts of organic acids of at most 90%, at most 50%, at most 10%,or at most 5% of the total content of metals in metal salts of organicacids in the hydrocarbon feed. Organic acids that generally form metalsalts include, but are not limited to, carboxylic acids, thiols, imides,sulfonic acids, and sulfonates. Examples of carboxylic acids include,but are not limited to, naphthenic acids, phenanthrenic acids, andbenzoic acid. The metal portion of the metal salts may include alkalimetals (for example, lithium, sodium, and potassium), alkaline-earthmetals (for example, magnesium, calcium, and barium), Column 12 metals(for example, zinc and cadmium), Column 15 metals (for example arsenic),Column 6 metals (for example, chromium), or mixtures thereof.

In certain embodiments, the crude product has a total content of metalsin metal salts of organic acidsin a range from 0.1 wtppm to 50 wtppm, 3wtppm to 20 wtppm, or 10 wtppm to 1 wtppm.

In certain embodiments, API gravity of the crude product produced fromcontact of the hydrocarbon feed with catalyst, at the contactingconditions, is increased by at least 2, at least 3, at least 5, or atleast 10 relative to the API gravity of the hydrocarbon feed. In certainembodiments, API gravity of the crude product ranges from 7 to 40, 10 to30, or 12 to 25.

In certain embodiments, the crude product has a viscosity of at most90%, at most 80%, or at most 70% of the viscosity of the hydrocarbonfeed. In some embodiments, the viscosity of the crude product is at most1000, at most 500, or at most 100 cSt.

In some embodiments, the crude product has a sediment content of at most0.1% by weight of crude product. The sediment content of the crudeproduct may range from 0.0001% to 0.1% from 0.001% to 0.05%, or from0.005% to 0.01% by weight of crude product.

In some embodiments, the sulfur content of the crude product is at most90%, at most 80%, or at most 70% of the sulfur content of thehydrocarbon feed. In some embodiments the sulfur content of the crudeproduct is at least 0.02 grams per gram of crude product. The sulfurcontent of the crude product may range from 0.001 grams to 0.1 grams,from 0.005 to 0.08 grams or from 0.01 to 0.05 grams per gram of crudeproduct.

In some embodiments, the nitrogen content of the crude product is 70% to130%, 80% to 120%, or 90% to 110% of the nitrogen content of thehydrocarbon feed.

In some embodiments, the crude product has a nitrogen content at least0.02 grams of nitrogen per gram of crude product. In some embodiments,the nitrogen content of the crude product may range from 0.001 grams to0.1 grams, from 0.005 grams to 0.08 grams, or from 0.01 to 0.05 gramsper gram of crude product.

In some embodiments, the crude product includes, in its molecularstructures, from 0.05 grams to 0.15 grams or from 0.09 grams to 0.13grams of hydrogen per gram of crude product. The crude product mayinclude, in its molecular structure, from 0.8 grams to 0.9 grams or from0.82 grams to 0.88 grams of carbon per gram of crude product. A ratio ofatomic hydrogen to atomic carbon (H/C) of the crude product may bewithin 70% to 130%, 80% to 120%, or 90% to 110% of the atomic H/C ratioof the hydrocarbon feed. A crude product atomic H/C ratio within 10% to30% of the hydrocarbon feed atomic H/C ratio indicates that uptakeand/or consumption of hydrogen in the process is relatively small,and/or that hydrogen is produced in situ.

The crude product includes components with a range of boiling points. Insome embodiments, the crude product includes, per gram of the crudeproduct: at least 0.001 grams, or from 0.001 grams to 0.5 grams ofhydrocarbons with a boiling range distribution of at most 100° C. at0.101 MPa; at least 0.001 grams, or from 0.001 grams to 0.5 grams ofhydrocarbons with a boiling range distribution between 100° C. and 200°C. at 0.101 MPa; at least 0.001 grams, or from 0.001 grams to 0.5 gramsof hydrocarbons with a boiling range distribution between 200° C. and300° C. at 0.101 MPa; at least 0.001 grams, or from 0.001 grams to 0.5grams of hydrocarbons with a boiling range distribution between 300° C.and 400° C. at 0.101 MPa; and at least 0.001 grams, or from 0.001 grams0.5 grams of hydrocarbons with a boiling range distribution between 400°C. and 538° C. at 0.101 MPa.

In some embodiments the crude product includes, per gram of crudeproduct, at least 0.001 grams of hydrocarbons with a boiling rangedistribution of at most 100° C. at 0.101 MPa and/or at least 0.001 gramsof hydrocarbons with a boiling range distribution between 100° C. and200° C. at 0.101 MPa.

In some embodiments, the crude product has a distillate content of atleast 110%, at least 120%, or at least 130% of the distillate content ofthe hydrocarbon feed. The distillate content of the crude product maybe, per gram of crude product, in a range from 0.00001 grams to 0.6grams (0.001-60 wt %), 0.001 grams to 0.5 grams (0.1-50 wt %), or 0.01grams to 0.4 grams (1-40 wt %).

In certain embodiments, the crude product has a VGO content, boilingbetween 343° C. to 538° C. at 0.101 MPa, of 70% to 130%, 80% to 120%, or90% to 110% of the VGO content of the hydrocarbon feed. In someembodiments, the crude product has, per gram of crude product, a VGOcontent in a range from 0.00001 grams to 0.8 grams, 0.001 grams to 0.7grams, 0.01 grams to 0.6 grams, or 0.1 grams to 0.5 grams.

In some embodiments, the crude product has a residue content of at most90%, at most 80%, or at most 50% of the residue content of thehydrocarbon feed. The crude product may have, per gram of crude product,a residue content in a range from in a range from 0.00001 grams to 0.8grams, 0.001 grams to 0.7 grams, 0.01 grams to 0.6 grams, 0.05 grams to0.5 grams, or 0.1 to 0.3 grams.

In some embodiments, the crude product has a total C₅ and C₇ asphaltenescontent of at most 90%, at most 80%, at most 75%, or at most 50% of thetotal C₅ and C₇ asphaltenes content of the hydrocarbon feed. In otherembodiments, the C₅ asphaltenes content of the hydrocarbon feed is atleast 10%, at least 30%, or at least 40% of the C₅ asphaltenes contentof the hydrocarbon feed. In certain embodiments, the crude product has,per gram of hydrocarbon feed, a total C₅ and C₇ asphaltenes contentranging from 0.001 grams to 0.2 grams, 0.01 to 0.15 grams, or 0.05 gramsto 0.15 grams.

In certain embodiments, the crude product has a MCR content of at most95%, at most 90%, or at most 80% of the MCR content of the hydrocarbonfeed. In some embodiments, decreasing the C₅ asphaltenes content of thehydrocarbon feed while maintaining a relatively stable MCR content mayincrease the stability of the hydrocarbon feed/total product mixture.The crude product has, in some embodiments, from 0.0001 grams to 0.20grams, 0.005 grams to 0.15 grams, or 0.01 grams to 0.010 grams of MCRper gram of crude product.

In some embodiments, the crude product is a hydrocarbon composition thathas a total Ni/Fe/V content of at least 150 wtppm; a residue content ofat least 0.1 grams per gram of hydrocarbon composition; a distillatecontent of at least 0.1 grams per gram of hydrocarbon composition, anoxygen content of at most 0.1 grams per gram of hydrocarbon composition;a micro-carbon residue content of at least 0.05 grams per gram ofhydrocarbon composition, and has a viscosity of at most 100 cSt at 37.8°C.

In some embodiments, the crude product includes from greater than 0grams, but less than 0.01 grams, 0.000001 grams to 0.001 grams, or0.00001 grams to 0.0001 grams of total catalyst per gram of crudeproduct. The catalyst present in the crude product may assist instabilizing the crude product during transportation and/or treatment.The catalyst in the crude product may inhibit corrosion, inhibitfriction, and/or increase water separation abilities of the crudeproduct. Methods described herein may be configured to add one or morecatalysts described herein to the crude product during treatment.

It may be desirable to only selectively reduce one or more components(for example, residue and/or viscosity) in a hydrocarbon feed withoutsignificantly changing the amount of Ni/V/Fe and/or sulfur in thehydrocarbon feed. In this manner, hydrogen uptake during contacting maybe “concentrated” on residue reduction, and not reduction of othercomponents. Since less of such hydrogen is also being used to reduceother components in the hydrocarbon feed, the amount of hydrogen usedduring the process may be minimized. For example, a disadvantaged crudemay have a high residue, but a Ni/V/Fe content that is acceptable tomeet treatment and/or transportation specifications. Such hydrocarbonfeed may be more efficiently treated by reducing residue without alsoreducing Ni/V/Fe.

In some embodiments, contact of a hydrocarbon feed using the catalystsdescribed herein at temperatures and pressures described herein producesa crude product that has a viscosity of at most 100 cSt at 37.8° C., atotal Ni/Fe/V content of at least 150 wtppm, a residue content of atleast 0.1 grams per gram of crude product, a distillate content of atleast 0.1 grams per gram of crude product, an oxygen content of at most0.1 grams per gram of crude product, and a micro-carbon residue contentof at least 0.05 grams per gram of crude product.

Catalysts used in one or more embodiments of the inventions may includeone or more bulk metals and/or one or more metals on a support. Themetals may be in elemental form or in the form of a compound of themetal. The catalysts described herein may be introduced into thecontacting zone as a precursor, and then become active as a catalyst inthe contacting zone (for example, when sulfur and/or a hydrocarbon feedcontaining sulfur is contacted with the precursor).

In some embodiments, catalysts used to change properties of thehydrocarbon feed include one or more Columns 6-10 metals on a support.Columns 6-10 metal(s) include, but are not limited to, chromium,molybdenum, tungsten, manganese, technetium, rhenium, iron, cobalt,nickel, ruthenium, palladium, rhodium, osmium, iridium, platinum, ormixtures thereof. The catalyst may have, per gram of catalyst, a totalColumns 6-10 metal(s) content in a range from at least 0.0001 grams, atleast 0.001 grams, at least 0.01 grams, or in a range of 0.0001 grams to0.6 grams, 0.001 grams to 0.3 grams, 0.005 grams to 0.1 grams, or 0.01grams to 0.08 grams.

In some embodiments, the catalyst includes Column 15 element(s) inaddition to the Columns 6-10 metal(s). Examples of Column 15 elementsinclude phosphorus. The catalyst may have a total Column 15 elementcontent, per gram of catalyst, in range from 0.000001 grams to 0.1grams, 0.00001 grams to 0.06 grams, 0.00005 grams to 0.03 grams, or0.0001 grams to 0.001 grams.

In certain embodiments, the catalyst includes Column 6 metal(s). Column6 metal(s) include, but are not limited to, chromium, molybdenum,tungsten, or mixtures thereof. The catalyst may have, per gram ofcatalyst, a total Column 6 metal(s) content of at least 0.00001 grams,at least 0.01 grams, at least 0.02 grams and/or in a range from 0.0001grams to 0.6 grams, 0.001 grams to 0.3 grams, 0.005 grams to 0.1 grams,or 0.01 grams to 0.08 grams. In some embodiments, the catalyst includesfrom 0.0001 grams to 0.06 grams of Column 6 metal(s) per gram ofcatalyst. In some embodiments, compounds of Column 6 metal(s) includeoxides such as molybdenum trioxide and/or tungsten trioxide. In certainembodiments, the catalyst includes only Column 6 metals or only Column 6compounds. In an embodiment, the catalyst includes only molybdenumand/or molybdenum oxides. In one embodiment the Column 6-10 metalcatalyst comprises at least 0.1 grams of molybdenum per gram ofcatalyst.

In some embodiments, the catalyst includes a combination of Column 6metal(s) with one or more metals from Columns 7-10. Columns 7-10metal(s) include, but are not limited to, manganese, technetium,rhenium, iron, cobalt, nickel, ruthenium, palladium, rhodium, osmium,iridium, platinum, or mixtures thereofin some embodiments, the catalysthas at most 0.03 grams, at most 0.02 grams or 0.01 grams of Columns 7-10metals per gram of catalyst. In some embodiments, the catalyst does notinclude Columns 7-10 metals.

A molar ratio of Column 6 metal to Columns 7-10 metal may be in a rangefrom 0.1 to 20, 1 to 10, or 2 to 5. In other embodiments, the catalystincludes Column 6 metal(s) and Column 10 metal(s). A molar ratio of thetotal Column 10 metal to the total Column 6 metal in the catalyst may bein a range from 1 to 10, or from 2 to 5.

Columns 6-10 metal(s) are incorporated with a support to form thecatalyst. In certain embodiments, Columns 6-10 metal(s) in combinationwith Column 15 element(s) are incorporated with a support to form thecatalyst. In embodiments in which the metal(s) and/or element(s) aresupported, the weight of the catalyst includes all support, allmetal(s), and all element(s). In some embodiments, the support includesrefractory oxides, porous carbon based materials, zeolites, orcombinations thereof. Refractory oxides may include, but are not limitedto, alumina, silica, silica-alumina, titanium oxide, zirconium oxide,magnesium oxide, or mixtures thereof. Supports may be obtained from acommercial manufacturer such as Criterion Catalysts and Technologies LP(Houston, Tex., U.S.A.). Porous carbon based materials include, but arenot limited to, activated carbon and/or porous graphite. Examples ofzeolites include Y-zeolites, beta zeolites, mordenite zeolites, ZSM-5zeolites, and ferrierite zeolites. Zeolites may be obtained from acommercial manufacturer such as Zeolyst (Valley Forge, Pa., U.S.A.).

In certain embodiments, the support includes gamma alumina, deltaalumina, alpha alumina, or combinations thereof. The amount of gammaalumina, delta alumina, alpha alumina, or combinations thereof, per gramof catalyst support, may be in a range from 0.0001 grams to 0.99 grams,0.001 grams to 0.5 grams, 0.01 grams to 0.1 grams, or at most 0.1 gramsas determined by x-ray diffraction. In some embodiments, the supportincludes from 0.0001 grams to 0.10 grams, 0.001 grams to 0.05 grams, or0.01 grams to 0.03 grams of silica; and 0.90 grams to 0.9999 grams, 0.95grams to 0.999 grams, or 0.99 to 0.97 grams of alumina.

One or more metals from Columns 6-10 of the Periodic Table and/or one ormore compounds of one or more metals from Columns 6-10 of the PeriodicTable may be co-mulled with a support to form a mixture. The mixture maybe formed into particles.

Catalysts that have a large surface area with a minimal amount ofcatalytic metal (for example, Columns 6-10 metals) on the surface of thecatalyst may be prepared by comulling the catalytic metals with asupport. Comulling of the support and catalytic metal may form asubstantially uniform or homogeneous mixture. In some embodiments, waterand/or solvent may be added to facilitate forming the mixture into apaste that may be extruded or formed into extrudate particles,spheroids, pills, tablets, cylinders, irregular extrusions or looselybound aggregates or clusters, by any known extrusion, molding tableting,pressing, pelletizing, or tumbling methods.

The Columns 6-10 metal(s) and support may be comulled with suitablemixing equipment. If more than one metal is present the metals may beadded together or separately. Examples of suitable mixing equipmentinclude tumblers, stationary shells or troughs, Muller mixers (forexample, batch type or continuous type), impact mixers, and any othergenerally known mixer, or generally known device, that will suitablyprovide the Columns 6-10 metal(s)/support mixture. In certainembodiments, the materials are mixed until the Columns 6-10 metal(s) is(are) substantially homogeneously dispersed in the support. Dispersionof the Columns 6-10 metal(s) in the support may inhibit coking of theColumns 6-10 metal(s) at high temperatures and/or pressures, thusallowing hydrocarbon feeds containing significant amounts of residueand/or high viscosities to be processed at rates, temperatures andpressures not obtainable by using conventional catalysts made usingimpregnation techniques. In some embodiments, comulling of a supportcontaining silica and Column 6-10 metal(s) forms a smoother catalystsurface.

Co-mulling the Column 6 metal(s) alone or in combination with Columns7-10 metal(s) with the support allows (in contrast to impregnation of asupport) at least a portion of the metal(s) to reside under the surfaceof the embedded metal catalyst (for example, embedded in the support),leading to less metal on the surface than would otherwise occur in theunembedded metal catalyst. In some embodiments, having less metal on thesurface of the catalyst extends the life and/or catalytic activity ofthe catalyst by allowing at least a portion of the metal to move to thesurface of the catalyst during use. The metals may move to the surfaceof the catalyst through erosion of the surface of the catalyst duringcontact of the catalyst with a hydrocarbon feed.

Without wishing to be bound by any kind of theory, intercalation and/ormixing of the components of the catalysts may change the structuredorder of the Column 6-10 metal in the Column 6-10 metal oxide crystalstructure to a substantially random order of Column 6-10 metal in thecrystal structure of the embedded catalyst. The order of the Column 6-10metal may be determined using powder x-ray diffraction methods. Theorder of elemental metal in the catalyst relative to the order ofelemental metal in the metal oxide may be determined by comparing theorder of the Column 6-10 metal peak in an x-ray diffraction spectrum ofthe Column 6-10 metal oxide to the order of the Column 6-10 metal peakin an x-ray diffraction spectrum of the catalyst. From broadening and/orabsence of patterns associated with Column 6-10 metal in an x-raydiffraction spectrum, it is possible to estimate that the Column 6-10metal(s) are substantially randomly ordered in the crystal structure.For example, molybdenum trioxide and the alumina support having a medianpore diameter of at least 180 Å may be combined to form analumina/molybdenum trioxide mixture. Molybdenum trioxide has a definitepattern (for example, definite D₀₀₁, D₀₀₂ and/or D₀₀₃ peaks). Thealumina/molybdenum trioxide mixture may be heat treated at a temperatureof at least 316° C. (600° F.), at least 427° C. (800° F.), or at least538° C. (1000° F.) to produce a catalyst that does not exhibit a patternfor molybdenum trioxide in an x-ray diffraction spectrum (for example,an absence of the D₀₀₁ peak).

Co-mulling the Columns 6-10 metal(s) with the support forms a Columns6-10 metal(s)/support mixture. In some embodiments, an acid and/or wateris added to the Columns 6-10 metal(s)/support mixture to assist information of the mixture into particles. The water and/or dilute acidare added in such amounts, and by such methods, as required to give themixture a desired consistency suitable to be formed into particles.Examples of acids include, but are not limited to, nitric acid, aceticacid, sulfuric acid, and hydrochloric acid.

The Columns 6-10 metal(s)/support mixture may be formed into particlesusing known techniques in the art such as extrusion. The particles(extrudates) may be cut using known catalyst cutting methods to formparticles. The particles may be heat treated (dried) at a temperature ina range from 65° C. to 260° C. or from 85° C. to 235° C. for a period oftime (for example, for 0.5-8 hours or 1-5 hours) and/or until themoisture content of the particle has reached a desired level.

The Column 6-10 metal/support and/or the Column 6-10 metal/supportparticles may be calcined in the presence of hot air and/or oxygen richair at a temperature in a range between 315° C. and 760° C., between535° C. and 700° C., or between 500° C. and 680° C. for a period of time(for example 0.5-8 hours or 1 to 5 hours) to remove volatile matter suchthat at least a portion of the Columns 6-10 metals are converted to thecorresponding metal oxide. The temperature conditions at which theparticles are calcined may be such that the pore structure of the finalcalcined mixture is controlled to form the pore structure and surfaceareas of the catalysts described herein. Calcining at temperaturesgreater than 760° C. may increase the pore volume of the catalyst, thuschange the distribution of pores and the surface area such that thecatalyst is not as effective in removing compounds that contribute tohigh viscosity and/or residue.

Contact of a hydrocarbon feed having undesirable properties (forexample, an undesirable viscosity, API gravity, MCR content, asphaltenecontent, metals content and/or residue content) with a Columns 6-10metal(s) catalysts having stacked structures (for example, catalystsformed using impregnation techniques) may require elevated temperaturesand/or pressures to produce a crude product with selected properties.The elevated temperatures or pressures allow minimal contact of thecatalyst with hydrocarbon feed so that the catalyst does not becomedeactivated. Contact of the catalyst with feeds having high residuecontents may shorten catalyst life due to the high molecular weightcompounds and/or metals in the hydrocarbon feed plugging the pores ofthe catalyst.

In contrast, contact of the feed with a catalyst with dispersed metalclusters (for example, a catalyst formed by comulling) that form adesired surface topology for the catalyst as described herein may allowadvantageous changes to the feed to occur at higher temperatures and/orlower pressures. This desired topology may allow the hydrocarbon feed tocontact the surface of the catalyst for longer periods of time withoutdeleterious effects to the active metal sites of the catalyst, thus thedispersed metal cluster catalyst may have a longer life than theconventional hydroprocessing catalyst at elevated temperatures and lowerpressures (for example, temperatures of at least 400° C. and pressuresof 3.8 MPa, 5 MPa, or 7 MPa). The selected topology catalyst may allow aprocess to be run without recharging or changing the catalyst, thus costof processing the hydrocarbon feed may be economically advantageous.

In some embodiments, catalysts may be characterized by pore structure.Various pore structure parameters include, but are not limited to, porediameter, pore volume, surface areas, or combinations thereof. Thecatalyst may have a distribution of total quantity of pore sizes versuspore diameters. The median pore diameter of the pore size distributionof the catalyst of the present invention may be in a range from 105 Å to150 Å, 110 Å to 130 Å, or 110 Å to 120 Å. In some embodiments, thecatalyst has a pore size distribution with a median pore diameter in arange from 105 Å to 150 Å, 110 Å to 130 Å, or 110 Å to 120 Å, with atleast 60% of a total number of pores in the pore size distributionhaving a pore diameter within 60 Å, 45 Å, 35 Å, or 25 Å of the medianpore diameter.

In some embodiments, the pore volume in pores of the catalyst of thepresent invention may be at least 0.3 cm³/g, at least 0.7 cm³/g, or atleast 0.9 cm³/g. In certain embodiments, the pore volume in pores of thecatalyst of the present invention may range from 0.3 cm³/g to 0.99cm³/g, 0.4 cm³/g to 0.8 cm³/g, or 0.5 cm³/g to 0.7 cm³/g.

The pore volume of the catalyst includes pores having a pore diameterbetween 1 Å and 5000 Å and pores having a pore diameter greater than5000 Å. In some embodiments, the catalyst has a majority of its porevolume in pores having a pore diameter of at most 600 Å, at most 500 Å,at most 300 Å, or at most 200 Å.

In some embodiments, the catalyst may have a pore size distribution witha median pore diameter in a range from about 105 Å to 150 Å, with atleast 60% of the total number of pores in the pore size distributionhaving a pore diameter within 60 Å of the median pore diameter, with atleast 50% of its pore volume in pores having a pore diameter of at most600 Å, and between 5% and 25% of its pore volume in pores having a porediameter between 1000 Å and 5000 Å.

In some embodiments the catalyst has at most 10%, at most 5% or at most4% of its pore volume in pores of at least 5000 Å.

The catalyst of the present invention may have a surface area of atleast 200 m²/g. Such surface area may be in a range from 250 m²/g to 500m²/g, or 260 m²/g to 400 m²/g.

Catalysts having specific surface topology, large surface areas and poredistributions described above may exhibit enhanced run times incommercial applications at low pressures and elevated temperatures. Forexample, the catalyst may remain catalytically active after at least 1year of run time. The enhanced run times may be attributed to the highsurface area of the catalyst and/or the narrow distribution of porediameter in the pore volume of the catalyst. Thus, the metals of thecatalyst remain exposed for longer periods of time and plugging of thepores of the catalyst is minimal. The high surface area and selecteddistribution of pores in the pore volume of the catalyst allowsprocessing of high viscosity and/or high residue crudes that would notbe able to be processed with conventional catalysts having the same poredistribution, but smaller surface area. Calcining a comulled catalyst attemperatures ranging from 315° C. to 760° C. may facilitate formation ofpores having similar pore diameters and narrow pore distributions withlarge surface areas.

In certain embodiments, the catalyst exists in shaped forms, forexample, pellets, cylinders, and/or extrudates. In some embodiments, thecatalyst and/or the catalyst precursor is sulfided to form metalsulfides (prior to use) using techniques known in the art (for example,ACTICAT™ process, CRI International, Inc.). In some embodiments, thecatalyst may be dried then sulfided. Alternatively, the catalyst may besulfided in situ by contact of the catalyst with a hydrocarbon feed thatincludes sulfur-containing compounds. In-situ sulfurization may utilizeeither gaseous hydrogen sulfide in the presence of hydrogen, orliquid-phase sulfurizing agents such as organosulfur compounds(including alkylsulfides, polysulfides, thiols, and sulfoxides). Ex-situsulfurization processes are described in U.S. Pat. No. 5,468,372 toSeamans et al., and U.S. Pat. No. 5,688,736 to Seamans et al., all ofwhich are incorporated herein by reference.

In certain embodiments, the catalyst is obtainable by co-mulling Column6-10 metal(s) with a support. Co-mulling the Column 6 metal(s) with thesupport may form a mixture or a substantially homogeneous mixture. Insome embodiments, the mixture may be extruded and/or dried. The mixturemay be calcined at a temperature of between 315° C. and 700° C. toproduce the catalyst.

The support may include alumina, silica, alumina-silica, titanium oxide,zirconium oxide, magnesium oxide, or mixtures thereof.

The catalyst may have from 0.001 grams to 0.3 grams, 0.005 grams to 0.2grams, or 0.01 grams to 0.1 grams of Column 6-10 metal(s) per gram ofcatalyst. In some embodiments, the catalyst may include at least 0.1grams of Column 6 metal(s) per gram of catalyst. In some embodiments,the catalyst may include at least 0.05 grams to 0.2 grams of Column 6metal(s) per gram of catalyst. In some embodiments, the catalyst mayinclude from 0.001 grams to 0.1 grams, 0.005 to 0.05 grams, or from 0.01grams to 0.03 grams of Column 10 metal(s) per gram of catalyst. Incertain embodiments, the catalyst may include from 0.001 grams to 0.1grams, 0.005 to 0.05 grams, or from 0.01 grams to 0.03 grams of Column 9metal(s) per gram of catalyst.

Such comulling of metal and support, followed by calcination, mayproduce a bimodal catalyst having a pore size distribution with a medianpore diameter ranging from 105 Å to 150 Å with at least 45 % or at least60% of the total number of pores in the pore size distribution having apore diameter within at least 60 Å of the median pore diameter, with atleast 50% of its pore volume in pores having a pore diameter of at most600 Å, and between 5% and 25% of its pore volume in pores having a porediameter between 1000 Å and 5000 Å.

In some embodiments, the catalyst may have a median pore diameter from110 Å and 130 Å.

In some embodiments, the catalyst may have a median pore diameter of atmost 120 Å, with at least 60% of a total number of pores in the poresize distribution having a pore diameter within 60 Å, with at least 50%of its pore volume in pores having a pore diameter from 105 Å to 150 Å,between 5% and 25% of its pore volume in pores having a pore diameterbetween 1000 Å and 5000 Å.

The catalyst may have a surface area of from 250 m²/g to about 300 m²/gand a pore volume about 0.7 cc/g.

This catalyst may reduce at least a portion of the components thatcontribute to higher viscosities, a portion of the components thatcontribute to residue, and/or a portion of the oxygen-containingcompounds. Treatment of the hydrocarbon feed with a bimodal Columns 6-10metal catalyst with a selected pore distribution may be economicaladvantageous since it allows production of a product with reducedviscosity with low hydrogen consumption.

The catalyst of the application may produce a crude product with a lowerviscosity as compared to the hydrocarbon feed with low hydrogenconsumption. In some embodiments, at contacting conditions at a totalpressure of 3.5 MPa, hydrogen consumption may be at most 60 Nm³/m³, atmost 50 Nm³/m³, or at most 30 Nm³/m³. In some embodiments, at contactingconditions at a total pressure of 3.5 MPa, hydrogen consumption may befrom 1 Nm³/m³ to 60 Nm³/m³, from 1 Nm³/m³ to 50 Nm³/m³, or from 5 Nm³/m³to 30 Nm³m³.

Using the catalyst(s) of this application and controlling operatingconditions may allow a crude product to be produced that has selectedproperties changed relative to the hydrocarbon feed while otherproperties of the hydrocarbon feed are not significantly changed. Theresulting crude product may have enhanced properties relative to thehydrocarbon feed and, thus, be more acceptable for transportation and/orrefining.

Arrangement of two or more catalysts in a selected sequence may controlthe sequence of property improvements for the feed. For example, APIgravity, at least a portion of the C₅ asphaltenes, at least a portion ofmetals in metal salts of organic acids, at least a portion of the iron,at least a portion of the nickel, and/or at least a portion of thevanadium or molybdenum in the hydrocarbon feed can be reduced before atleast a portion of heteroatoms in the feed are reduced.

Arrangement and/or selection of the catalysts may, in some embodiments,improve lives of the catalysts and/or the stability of the hydrocarbonfeed/total product mixture. Improvement of a catalyst life and/orstability of the hydrocarbon feed/total product mixture duringprocessing may allow a contacting system to operate for at least 3months, at least 6 months, or at least 1 year without replacement of thecatalyst in the contacting zone.

Combinations of selected catalysts may allow reduction in at least aportion of the components that contribute to viscosity, at least aportion of the components that contribute to residue, at least a portionof the components that contribute to TAN, or combinations thereof, fromthe hydrocarbon feed before other properties of the hydrocarbon feed arechanged, while maintaining the stability of the hydrocarbon feed/totalproduct mixture during processing (for example, maintaining ahydrocarbon feed P-value of above 1.5). Alternatively, C₅ asphaltenes,and/or API gravity may be incrementally reduced by contact of thehydrocarbon feed with selected catalysts. The ability to incrementallyand/or selectively change properties of the hydrocarbon feed may allowthe stability of the hydrocarbon feed/total product mixture to bemaintained during processing.

In some embodiments, the catalyst (described above) may be positionedupstream of a series of catalysts. Such positioning of the catalyst mayallow removal of high molecular weight contaminants, and/or metals inmetal salts of organic acids, while maintaining the stability of thehydrocarbon feed/total product mixture.

The catalyst allows, in some embodiments, for removal of at least aportion of oxygen-containing compounds, removal of components thatcontribute to a decrease in the life of other catalysts in the system,or combinations thereof, from the hydrocarbon feed. For example,reducing at least a portion of C₅ asphaltenes in the hydrocarbonfeed/total product mixture relative to the hydrocarbon feed inhibitsplugging of other catalysts positioned downstream, and thus, increasesthe length of time the contacting system may be operated withoutreplenishment of catalyst. Reduction in viscosity may, in someembodiments, increase a life of one or more catalysts positioned afterthe catalyst described above.

In some embodiments, commercially available catalysts may be positioneddownstream and/or upstream of the catalyst described herein to reduceselected properties of the feed. For example, a demetallization catalystmay be positioned downstream and/or upstream of the catalyst to reducethe Ni/V/Fe content of the crude produce as compared to Ni/V/Fe of thefeed. A desulfurization catalyst may be positioned downstream of thecatalyst to reduce the sulfur-containing compounds content of the crudeproduct as compared to the sulfur-containing compounds content of thefeed.

The ability to deliver hydrogen to specified contacting zones tends tominimize hydrogen usage during contacting. Combinations of catalyst(s)that facilitate generation of hydrogen during contacting, and catalyststhat uptake a relatively low amount of hydrogen during contacting, maybe used to change selected properties of a crude product relative to thesame properties of the hydrocarbon feed. The order and/or number ofcatalyst(s) may be selected to minimize net hydrogen uptake whilemaintaining the hydrocarbon feed/total product stability. Minimal nethydrogen uptake allows residue content, VGO content, distillate content,API gravity, or combinations thereof of the hydrocarbon feed to bemaintained within 20% of the respective properties of the hydrocarbonfeed, while the API gravity and/or the viscosity of the crude product isat most 90% of the API gravity and/or the viscosity of the hydrocarbonfeed.

Reduction in net hydrogen uptake by the hydrocarbon feed may produce acrude product that has a boiling range distribution similar to theboiling point distribution of the hydrocarbon feed. The atomic H/C ratioof the crude product may also only change by relatively small amounts ascompared to the atomic H/C ratio of the hydrocarbon feed.

In some embodiments, catalyst selection and/or order of catalysts incombination with controlled contacting conditions (for example,temperature and/or hydrocarbon feed flow rate) may assist in reducinghydrogen uptake by the hydrocarbon feed, maintaining hydrocarbonfeed/total product mixture stability during processing, and changing oneor more properties of the crude product relative to the respectiveproperties of the hydrocarbon feed. Stability of the hydrocarbonfeed/total product mixture may be affected by various phases separatingfrom the hydrocarbon feed/total product mixture. Phase separation may becaused by, for example, insolubility of the hydrocarbon feed and/orcrude product in the hydrocarbon feed/total product mixture,flocculation of asphaltenes from the hydrocarbon feed/total productmixture, precipitation of components from the hydrocarbon feed/totalproduct mixture, or combinations thereof.

At certain times during the contacting period, the concentration ofhydrocarbon feed and/or total product in the hydrocarbon feed/totalproduct mixture may change. As the concentration of the total product inthe hydrocarbon feed/total product mixture changes due to formation ofthe crude product, solubility of the components of the hydrocarbon feedand/or components of the total product in the hydrocarbon feed/totalproduct mixture tends to change. For example, the hydrocarbon feed maycontain components that are soluble in the hydrocarbon feed at thebeginning of processing. As properties of the hydrocarbon feed change(for example, API gravity, viscosity, MCR, C₅ asphaltenes, P-value,sediment, or combinations thereof), the components may tend to becomeless soluble in the hydrocarbon feed/total product mixture. In someinstances, the hydrocarbon feed and the total product may form twophases and/or become insoluble in one another. Solubility changes mayalso result in the hydrocarbon feed/total product mixture forming two ormore phases. Formation of two phases, through flocculation ofasphaltenes, change in concentration of hydrocarbon feed and totalproduct, and/or precipitation of components, tends to reduce the life ofone or more of the catalysts. Additionally, the efficiency of theprocess may be reduced. For example, repeated treatment of thehydrocarbon feed/total product mixture may be necessary to produce acrude product with desired properties.

During processing, the P-value and/or sediment value of the hydrocarbonfeed/total product mixture may be monitored and the stability of theprocess, hydrocarbon feed, and/or hydrocarbon feed/total product mixturemay be assessed. Typically, a P-value that is at most 1.0 indicates thatflocculation of asphaltenes from the hydrocarbon feed generally occurs.If the P-value is initially at least 1.0, and such P-value increases oris relatively stable during contacting, then this indicates that thehydrocarbon feed is relatively stabile during contacting. Hydrocarbonfeed/total product mixture stability, as assessed by P-value, may becontrolled by controlling contacting conditions, by selection ofcatalysts, by selective ordering of catalysts, or combinations thereof.Such controlling of contacting conditions may include controlling LHSV,temperature, pressure, hydrogen uptake, hydrocarbon feed flow, orcombinations thereof.

Monitoring a sediment value during processing may indicate formation ofhigh molecular compounds, precipitation of high molecular compounds, orprecipitation of metals. A sediment value that decreases or isrelatively stable during contacting indicates that the hydrocarbon feedis relatively stable during contacting.

During processing, the inlet pressure of a contacting zone of a fixedbed reactor may be monitored. A rapid increase in inlet pressure mayindicate that flow through the catalyst is inhibited. The inhibition offlow may be caused by an increase in deposit or sediment formation. Theincrease in deposit or sediment may plug pores of the catalyst, thusrestricting flow of the hydrocarbon feed through the contacting zone.

Typically, hydrocarbon feed having viscosities that inhibit thehydrocarbon feed from being transported and/or pumped are contacted witha catalyst at elevated hydrogen pressures (for example, at least 7 MPa,at least 10 MPa or at least 15 MPa) to produce products that are morefluid. At elevated hydrogen pressures coke formation is inhibited, thusthe properties of the hydrocarbon feed may be changed with minimal cokeproduction. Since reduction of viscosity, residue and C₅/C₇ asphaltenesis not dependent on hydrogen pressure reduction of these properties maynot occur unless the contacting temperature is at least 300° C. For somehydrocarbon feeds, temperatures of at least 350° C. may be required toreduce desired properties of the hydrocarbon feed to produce a productthat meets the desired specifications. At increased temperatures cokeformation may occur, even at elevated hydrogen pressures. As theproperties of the hydrocarbon feed are changed, the P-value of thehydrocarbon feed/total product may decrease below 1.0 and/or sedimentmay form, causing the product mixture to become unstable. Since,elevated hydrogen pressures require large amounts of hydrogen, a processcapable of reducing properties that are independent of pressure atminimal temperatures is desirable.

Contact of a hydrocarbon feed having a viscosity of at least 10 cSt at37.8° C. (for example, at least 100 cSt, at least 1000 cSt, or at least2000 cSt) in a controlled temperature range of 370° C. to 450° C., 390°C. to 440° C., or from 400 ° C. to 430° C. at pressures of 3.5 MPa, 5MPa, or 7 MPa with the catalyst described herein produces a crudeproduct having changed properties (for example, viscosity, residue andC₅/C₇ asphaltenes) of at most 50%, at most 30%, at most 20%, at most10%, or at most 1% of the respective property of the hydrocarbon feed.During contact, the P-value remains may be kept above 1.0 by controllingthe contacting temperature. For example, in some embodiments, if thetemperature increases above 450° C., the P-value drops below 1.0 and thehydrocarbon feed/total product mixture becomes unstable. If thetemperature decreases below 370° C., minimal changes to the hydrocarbonfeed properties occur.

In some embodiments, contacting temperatures are controlled such that C₅asphaltenes and/or other asphaltenes are removed while maintaining theMCR content of the hydrocarbon feed. Reduction of the MCR contentthrough hydrogen uptake and/or higher contacting temperatures may resultin formation of two phases that may reduce the stability of thehydrocarbon feed/total product mixture and/or life of one or more of thecatalysts. Control of contacting temperature and hydrogen uptake incombination with the catalysts described herein allows the C₅asphaltenes to be reduced while the MCR content of the hydrocarbon feedonly changes by a relatively small amount.

In some embodiments, contacting conditions are controlled such that thetotal partial pressure of the contacting zone is maintained at a desiredpressure, at a set flow rate and elevated temperatures (for example,temperatures of at least 200° C., at least 300° C., or at least 400°C.). The ability to operate at a total pressure of at most 5 MPa or atmost 3.5 MPa allows an increase in LHSV (for example an increase to atleast 0.5 h⁻¹, at least 1 h⁻¹, at least 2 h⁻¹, at least 5 h⁻¹, or atleast 10 h⁻¹) with the same or longer catalyst life as contacting attotal pressures of at most 5 MPa or at most 3.5 MPa. Operating at lowerpartial pressures of hydrogen or lower total pressure decreases the costof the operation and allows contacting to be performed where limitedamounts of hydrogen are available. In some embodiments, the totalpressure is the same as the total partial pressure of hydrogen being fedto the contacting zone.

The crude product produced by contacting a hydrocarbon feed with one ormore catalysts described herein may be useful in a wide range ofapplications including, but not limited to, use a feed to refineries,feed for producing transportation fuel, a diluent, or an enhancing agentfor underground oil recovery processes. For example, hydrocarbon feedshaving an API gravity of at most 10 (for example, bitumen and/or heavyoil/tar sands crude) may be converted into various hydrocarbon streamsthrough a series of processing steps using cracking units (for example,an ebullating bed cracking unit, a fluid catalytic cracking unit,thermal cracking unit, or other units known to convert hydrocarbon feedto lighter components).

Reduction of the viscosity and/or residue content of a hydrocarbon feedto produce a feed stream that may be processed in a cracking unit mayenhance the processing rate of hydrocarbon feed. A system using themethods and catalysts described herein to change properties of ahydrocarbon feed may be positioned upstream of one or more crackingunits. Treatment of the hydrocarbon feed in one or more systemsdescribed herein may produce a feed that improves the processing rate ofthe cracking unit by at least a factor of 2, at least a factor of 4, atleast a factor of 10, or at least a factor of 100. For example, a systemfor treating a hydrocarbon feed having a viscosity of at least 100 cStat 37.8° C. and/or 0.1 grams of residue per gram of hydrocarbon feed mayinclude one or more contacting systems described herein positionedupstream of a cracking unit. The contacting system may include one ormore catalysts described herein capable of producing a crude producthaving a viscosity of at most 50% of the viscosity of the hydrocarbonfeed at 37.8° C. and/or at most 90% of the residue of the hydrocarbonfeed. The crude product and/or a mixture of the crude product andhydrocarbon feed may enter a cracking unit. Since the crude productand/or mixture of the crude product and hydrocarbon feed has a lowerviscosity than the original hydrocarbon feed, the processing ratethrough the cracking unit may be improved.

In some embodiments, hydrocarbon feeds having at least 0.01 grams of C₅asphaltenes may be deasphalted prior to hydroprocessing treatment in arefinery operation. Deasphalting processes may involve solventextraction and/or contacting the crude with a catalyst to removeasphaltenes. Reduction of at least a portion of the components thatcontribute to viscosity, at least a portion of the components thatcontribute to residue and/or asphaltenes prior to the deasphaltingprocess may eliminate the need for solvent extraction, reduce the amountof required solvent, and/or enhance the efficiency of the deasphaltingprocess. For example, a system for treating a hydrocarbon feed having,per gram of hydrocarbon feed, at least 0.01 grams of C₅ asphaltenesand/or 0.1 grams of residue and a viscosity of at least 10 cSt at 37.8°C. may include one or more contacting systems described hereinpositioned upstream of an deasphalting unit. The contacting system mayinclude one or more catalysts described herein capable of producing acrude product having a C₅ asphaltenes content of at most 50% of thehydrocarbon feed C₅ asphaltenes content, a residue content of at most90% of the hydrocarbon feed residue content, a viscosity of at most 50%of the hydrocarbon viscosity or combinations thereof. The crude productand/or a mixture of the crude product and hydrocarbon feed may enter thedeasphalting unit. Since the crude product and/or mixture of the crudeproduct and the hydrocarbon feed has a lower asphaltene, residue and/orviscosity than the original hydrocarbon feed, the processing efficiencyof the deasphalting unit may be increased by at least 5%, at least 10%,at least 20% or at least 50% of the original efficiency.

EXAMPLES

Non-limiting examples of catalyst preparations and methods of using suchcatalysts under controlled contacting conditions are set forth below.

Example 1 Preparation of a Columns 6-10 Metal(s) Catalyst

A first solution was prepared by combining MoO₃ (789.96 grams),phosphoric acid (73.66 grams, 85.9 Mol %), and deionized water (2400grams) to form a slurry. The slurry was heated to 82° C. untildissolution of the solids.

To the slurry, Ni(OH)₂.(210.32 grams) was added at a rate to control anyobserved exotherm, and then heated to 96° C. until dissolution of thesolids. To the heated mixture was added citric acid monohydrate (5 Mol%, 200.46 grams) at a rate sufficient to control any observed exotherm.After addition of the citric acid the solution was heated to 100° C.until the molybdenum/nickel/phosphorus solution was transparent, andthen the volume of the molybdenum/nickel/phosphorus solution was reducedto 1249.80 grams.

To a muller, a support (4076.09 grams) that contained 0.02 grams ofsilica and 0.98 grams alumina per gram of support was added. With themuller running, the molybdenum/nickel/phosphorus solution (1249.80grams) was added to the support and the resulting mixture was mulled for25 minutes. Deionized water (211.90 grams) was added to themolybdenum/nickel/phosphorus/support mixture and the resulting mixturewas mulled 15 minutes. Additional deionized water (109.69 grams) wasadded to the mixture and the resulting mixture was mulled 20 minutes.The mulled molybdenum/nickel/phosphorus/support mixture had a pH of 5.05and a loss on ignition (measured after 1 hour at 700° C.) of 0.5689grams per gram of mixture.

The mulled mixture was extruded using 1.3 mm trilobe dies to form 1.3 mmtrilobe extrudate particles. The extrudate particles were dried at 125°C. for several hours and then calcined at 676.7° C. (1250° F.) for twohours. The catalyst contained 0.133 grams of molybdenum, 0.032 grams ofnickel and 0.005 grams of phosphorus with the balance being support. Thecatalyst had a pore size distribution with a median pore diameter of 117Å with 60% of the total number of pores in the pore size distributionhaving a pore diameter within 59 Å of the median pore diameter, a totalpore volume of 0.69 cc/g, a surface area of 277 m²/g. The pore sizedistribution measured using mercury porosimetry at a contact angle of140 is shown in TABLE 1.

TABLE 1 Pore Diameter % Pore in Å Volume  <70 6.24  70-100 26.43 100-13025.35 130-150 6.34 150-180 4.73 180-200 1.86 200-240 2.41 240-600 7.15 600-1000 2.6 1000-3000 7.2 3000-5000 6.7 >5000 3.17

This example demonstrates a catalyst that includes a support and one ormore metals from Columns 6-10 of the Periodic Table and/or one or morecompounds of one or more metals from Columns 6-10 of the Periodic Table.The catalyst has a surface area of at least 250 m²/g, a median porediameter ranging from 105 Å to 150 Å with at least 60% of the totalnumber of pores in the pore size distribution having a pore diameterwithin at least 60 Å of the median pore diameter, with at least 50% ofits pore volume in pores having a pore diameter of at most 600 Å, andbetween 5% and 25% of its pore volume in pores having a pore diameterbetween 1000 Å and 5000 Å.

Example 2 Contact of a Hydrocarbon Feed with a Column 6 Metal(s)Catalyst

A tubular reactor with a centrally positioned thermowell was equippedwith thermocouples to measure temperatures throughout a catalyst bed.The catalyst bed was formed by filling the space between the thermowelland an inner wall of the reactor with catalysts and silicon carbide(20-grid, Stanford Materials; Aliso Viejo, Calif.). Such silicon carbideis believed to have low, if any, catalytic properties under the processconditions described herein. The catalyst was blended with an equalvolume amount of silicon carbide before placing the mixture into thecontacting zone of the reactor.

The hydrocarbon feed flow to the reactor was from the top of the reactorto the bottom of the reactor. Silicon carbide was positioned at thebottom of the reactor to serve as a bottom support.

A Column 6 metal catalyst prepared as described in Example 1 was mixedwith silicone carbide (total of 50 cm³) was positioned in the contactingzone.

Silicon carbide was positioned on top of the top contacting zone to filldead space and to serve as a preheat zone. The catalyst bed was loadedinto a Lindberg furnace that included four heating zones correspondingto the preheat zone, the contacting zone, and the bottom support.

The catalyst was sulfided by introducing a gaseous mixture of 5 vol %hydrogen sulfide and 95 vol % hydrogen gas into the contacting zones ata rate of 1.5 liter of gaseous mixture per volume (mL) of total catalyst(silicon carbide was not counted as part of the volume of catalyst).Temperatures of the contacting zones were increased to 204° C. (400° F.)over 1 hour and held at 204° C. for 2 hours. After holding at 204° C.,the contacting zones were increased incrementally to 316° C. (600° F.)at a rate of 10° C. (50° F.) per hour. The contacting zones weremaintained at 316° C. for an hour, then incrementally raised to 370° C.(700° F.) over 1 hour and held at 370° C. for two hours. The contactingzones were allowed to cool to ambient temperature.

After sulfidation of the catalysts, the temperature of the contactingzones was raised to a temperature of 410° C. A hydrocarbon feed (PeaceRiver) having the properties listed in Table 2 was then contacted withthe catalysts. The hydrocarbon feed flowed through the preheat zone, topcontacting zone, bottom contacting zone, and bottom support of thereactor. The hydrocarbon feed was contacted with each of the catalystsin the presence of hydrogen gas. Contacting conditions were as follows:ratio of hydrogen gas to feed was 318 Nm³/m³ (2000 SCFB) and LHSV wasabout 0.5 h⁻¹. The two contacting zones were heated to 400° C. andmaintained between 400° C. and 420° C. at a pressure of 3.5 MPa (500psig) for 3436 hours as the hydrocarbon feed flowed through the reactor.

As shown in Table 2, the crude product had a viscosity of 58 cSt at37.8° C.

This example demonstrates that contact of a hydrocarbon feed with acatalyst that includes one or more metals from Columns 6 of the PeriodicTable and/or one or more compounds of one or more metals from Columns 6of the Periodic Table having a pore size distribution with a median porediameter in the range from 105 to 150 Å, with at least 50% of its porevolume in pores having a pore diameter of at most 130 Å, and between 10%and 20% of its pore volume in pores having a pore diameter between 1000Å and 5000 Å; at a pressure of 3.5 MPa produces a crude product having aviscosity content of at most 50% of hydrocarbon feed viscosity at 37.8°C. This example also demonstrates that a hydrocarbon feed having aviscosity of at least 1000 cSt at 37.8° C. may be contacted at lowpressures without plugging the catalyst and/or producing an unstableproduct. For example, the P-value during contacting was 1.2 and 0.007%of sediment by weight was produced.

Example 3 Contact of a Hydrocarbon Feed with a Column 6 Metal(s)Catalyst

The hydrocarbon feed, catalyst, contacting conditions, and sulfidationwere the same as Example 2 except that the pressure during operation(1389 hours) was about 7 MPa. As shown in Table 2, the crude product hada viscosity of 65 cSt at 37.8° C.

Comparison of the data from Examples 2 and 3 demonstrates thatcontacting of the hydrocarbon feed at a pressure of 3.5 MPa and attemperatures between 400° C. and 420° C. produces a crude product withenhanced viscosity reduction with less hydrogen consumption was observedas compared to the crude product obtained at higher pressure and thesame temperature. Operating at lower pressures provides an economicadvantage as less hydrogen is required to operate the contacting system.

Comparative Example

The hydrocarbon feed, contacting conditions, and sulfidation were thesame as Example 2.

A commercial bimodal molybdenum/nickel catalyst (RM 5030, CriterionCatalysts & Technologies, Houston, Tex., 24 cm³) used for upgradingresid was prepared, mixed with silicone carbide (30 cm³ for a totalcatalyst/silicone carbide mixture of 54 cm³), and the mixture waspositioned in the contacting zone. The run was terminated at 1872 hoursdue to a rapid increase in pressure change (inlet pressure of greaterthan 13 MPa (about 1872 psig). Rapid increase in pressure was attributedto the catalyst being plugged from high levels of sediment and/orprecipitation of some of the product due to the P-value being less than1.

In comparing Examples 2 and 3 with the comparative Example, the crudeproducts have similar values for all the Examples. The contact time forExamples 2 and 3 are significantly longer than the contact time for thecomparative example. As such, it may be concluded that the contact ofthe hydrocarbon feed with hydrogen in the presence of the bimodalcatalyst prepared as described in Example 1 may be done at low pressuresand high temperatures for longer periods of time than the comparativecatalyst at the same temperatures and pressures.

TABLE 2 Crude Product Example Property Feed 2 3 Comparative ContactTime, hours 3436 3436 1872 Pressure, MPa 3.5 MPa 7 MPa 3.5 MPa APIGravity 7.9 14.9 16.3 15.8 Density at 15.56° C. 1.0149 0.9633 0.95730.9608 (60° F.), g/cm³ Hydrogen, wt % 10.109 10.645 11.015 10.617Carbon, wt % 81.987 84.25 84.6 84.617 Sulfur, wt % 6.687 4.473 3.7013.782 Oxygen, wt % 0.62 0.27 0.315 * Nitrogen, wt % 0.366 0.362 0.3690.385 Nickel, wtppm 70 60 39 56 Iron, ppm 2.4 0.2 0.2 0.2 Vanadium,wtppm 205 180 90 152 Calcium, wtppm 6.7 1.4 0.3 2.1 Copper, wtppm 0.90.4 0.2 0.2 Chromium, wtppm 0.3 0.2 0.2 0.2 Silicon, wtppm 1.2 0.3 0.30.3 Magnesium, wtppm 0.8 0.4 0.2 0.4 Zinc, wtppm 6.0 0.9 0.7 1.7Molybdenum, wtppm 6.6 0.3 0.4 0.8 Micro-Carbon 12.5 10.3 9.0 9.6Residue, wt % C₅ Asphaltenes, wt % 16.2 7.5 6.0 8.0 C₇ Asphaltenes, wt %10.9 5.2 3.9 5.1 Naphtha, wt % 5.8 5.9 5.1 Distillate, wt % 15.0 29.529.4 30.7 VGO, wt % 37.5 39.6 40.2 39.8 Residue, wt % 47.4 25.1 24.524.4 P-Value 2.6 1.2 1.2 <1.0 Viscosity at 37.8° C. 8357 58 65 51.4(100° F.), cSt Hydrogen 55.17 104.5 * Consumption, Nm³/m³ Sediment, wt %0.007 0.008 plugged * Not Determined

1. A method of making a catalyst, comprising: co-mulling one or moremetals from Columns 6-10 of the Periodic Table and/or one or morecompounds of one or more metals from Columns 6-10 of the Periodic Tablewith a support to produce a metal/support composition; and calcining themetal/support composition at temperatures ranging from 315° C. to 760°C. to provide a calcined catalyst with a pore size distribution with amedian pore diameter ranging from 105 Å to 150 Å with at least 60% ofthe total number of pores in the pore size distribution having a porediameter within 60 Å of the median pore diameter, with at least 50% ofits pore volume in pores having a pore diameter of at most 600 Å, andbetween 5% and 25% of its pore volume in pores having a pore diameterbetween 1000 Å and 5000 Å, wherein pore diameters and pore volumes areas measured by ASTM Method D4284.
 2. A catalyst comprising: one or moremetals from Columns 6-10 of the Periodic Table and/or one or morecompounds of one or more metals from Columns 6-10 of the Periodic Table;wherein the catalyst has a median pore diameter ranging from 105 Å to150 Å with at least 60% of the total number of pores in the pore sizedistribution having a pore diameter within at least 60 Å of the medianpore diameter, with at least 50% of its pore volume in pores having apore diameter of at most 600 Å, and between 5% and 25% of its porevolume in pores having a pore diameter between 1000 Å and 5000 Å,wherein pore diameters and pore volumes are as measured by ASTM MethodD4284.
 3. The catalyst of claim 2, wherein the catalyst is bimodal. 4.The catalyst of claim 2, wherein the catalyst comprises a support, whichsupport includes from 0.0001 grams to 0.10 grams, of silica; and 0.90grams to 0.9999 grams of alumina.
 5. A method of producing a crudeproduct, comprising: contacting a hydrocarbon feed with one or morecatalysts to produce a total product that includes the crude product,wherein at least one of the catalysts comprises one or more metals fromColumns 6-10 of the Periodic Table and/or one or more compounds of oneor more metals from Columns 6-10 of the Periodic Table; wherein theColumn 6-10 metal catalyst has a median pore diameter ranging from 105 Åto 150 Å with at least 60% of the total number of pores in the pore sizedistribution having a pore diameter within at least 60 Å of the medianpore diameter, with at least 50% of its pore volume in pores having apore diameter of at most 600 Å, and between 5% and 25% of its porevolume in pores having a pore diameter between 1000 Å and 5000 Å,wherein surface area is as determined by ASTM Method D3663 and porediameters and pore volumes are as measured by ASTM Method D4284; andpore diameters and pore volumes are as measured by ASTM Method D4284. 6.The method of claim 5, wherein the crude product is a liquid mixture at25° C. and 0.101 MPa.
 7. The method of claim 5, wherein the hydrocarbonfeed has a viscosity of at least 100 cSt at 37.8° C. and the crudeproduct is a liquid mixture at 25° C. and 0.101 MPa, and the methodfurther comprises controlling contacting conditions such that the crudeproduct has a viscosity at 37.8° C. of at most 90% of the viscosity ofthe hydrocarbon feed at 37.8° C., wherein viscosity is as determined byASTM Method D445.
 8. The method of claim 5, further comprisescontrolling contacting conditions at a total pressure at most 5 MPa anda temperature of at least 200° C.
 9. The method of claim 5, wherein thecrude product has a sediment content of at most 0.01 gram per gram ofcrude product.
 10. The method of claim 5, wherein the method furthercomprises fractionating the crude product into one or more distillatefractions, and producing transportation fuel from at least one of thedistillate fractions.
 11. A crude product produced by the methods asclaimed in any of claims 5-10.
 12. A hydrocarbon composition comprising:a total Ni/Fe/V content of at least 150 wtppm as determined by ASTMMethod D5708; a residue content of at least 0.1 grams per gram ofhydrocarbon composition as determined by ASTM Method D5307; a distillatecontent of at least 0.1 grams per gram of hydrocarbon composition asdetermined by ASTM Method D5307; an oxygen content of at most 0.1 gramsper gram of hydrocarbon composition, as determined by ASTM Method E385;and a micro-carbon residue content of at least 0.05 grams per gram ofhydrocarbon composition as determined by ASTM Method D4530, and whereinthe hydrocarbon composition has a viscosity of at most 100 cSt at 37.8°C., wherein viscosity is as determined by ASTM Method D445.
 13. Atransportation fuel comprising one or more distillate fractions madefrom the crude product as claimed in claim 11 or the hydrocarboncomposition as claimed in claim
 12. 14. A diluent comprising one or moredistillate fractions made from the crude product as claimed in claim 11or the hydrocarbon composition as claimed in claim 12.